Azo compounds and material colored therewith



I the other materials iust mentioned.

fastness to light and made possible consists of Patented Jan. 11, 1944 .JUNITED STATES "Paras; O'FFE 1 2,338,709 V V 3 J azo COMPOUND s AND MATERIAL COLORED HEBEWITH Joseph B. Dickey, Rochester, N. Y.,' asslgnor to 1 Eastman Kodak Company, Rochester, N. 2., a corporation or New Jersey lilo Apnlioationoctober so, 1941, set-mm. 417,167

14 Claims. (on zoo-15o) Thisinvention' relates to new azo compounds and their application to the art of dyeing or coloring. Textile materials such as organicderivatives of cellulose, wool, silk, "Nylon" and Vinyon" andiacquers composed of cellulose esters,

cellulose ethers and vinyl derivatives, for example, can be colored. Coloration can be effectedby dyeing, printing, stencilling or other suitable 1 methods. 1

Typical organic derivatives or cellulose include the hydrolyzed as wellas the unhydrolyzed cellulose organic acid esters such as cellulose acetate, cellulose formate, cellulose propionate, or

the unhydrolyzed mixed organic acid esters or cellulose such as cellulose acetate-propionate, cellulose acetate-butyr'ate, and the cellulose ethers such as methyl cellulose, ethyl cellulose, or benzyl cellulose. more particularly'ln'connection with the colora- While my invention will be illustrated,

cellulose butyrate and-the hydrolyzed-as well as I tion of cellulose acetate, a material to which the invention is especially adapted, it will be understood that it applies equally to the coloration of It is an object, of my invention to provide a new class or azo compounds. Another object is to provide a process tor the dyeing or coloration of various textile materials including organic derivatives of cellulose, wool, silk, "Nylon and Vinyon textile materials. A further object-is to provide dyed textile materials which are of good washing. f Other objects will hereinafter appear.

The azo'compounds of my invention by means of which the above objects are accomplished 01:35

ing theiornaulat J J? theazo compounds havwherein R stands for a; member selected from the groupconsisting of a benzene'nucleus and an azobenzene' nucleus, R1 stands for a membe'r se lected from the group consisting of a benzene nucleus and a naphthalene nucleus, X stands for a piperidi'ne" nucleus joined through-it's nuclear nitrogen atomto a carbon atom of the member R1 which .is in para position to the azo bond,,OY stands for a member selected from thegroup consisting oi. a hydroxy group, a ONHr group, an I O-alkali-iorming metal, an alkoxy group, an

0(Il-alkyl group, a sulfate group, a phosphato group and a phosphito group and n stands for a member se- NOy-QNHi vvl'lerein Z and Z1 each stand for a member selected from the group consisting of hydrogen,

a halogen atom, a nitro group, a hydroxy group,

'an alkyl group, an, alkoxy group, an alkyl sulione group, a sulionamide group and a carboxyl group appear to be advantageous.

' The azo dye compounds of my invention yield a wide variety of shades. Depending upon the particular compo ents employed, orange, pink, blue, violet, red an rubine shades, for example, can

be obtained. ,Generallyspeakin'g, the colorations obtained are of excellent iastness .to light and washing and can be discharged to clear whites. For'the coloration of organic derivatives of cellulose nuclear non-sulfonated dye compounds which are preferably free of a nuclear carboxylic acid group in either" its free acid or salt form should be employed. Thenuclear non-sulionated 'dye compounds can likewise. be employed to' color the other materials named herein. The nuclear. sulfonatedcompoundspossess little or no applicability for the coloration of organic derivatives of cellulose but can be employed for the coloration of wool and silk by known methods for the coloration of these materials. These sulfonated compounds can be prepared, for example, by sulfonation of the unsulfonated'compounds.

The azo compounds of my invention on reduction yield p-amino-(phenyl or naphthyD-piperidines which are valuable as antioxidants for gasoline and as photographic developers in the preparation of colored photographic films.

v The azo compounds of my invention can be prepared by couplingdiazotized aniline and aminoazobenzene compounds with the coupling components having the formula:

wherein R1, X, CY and n have the meaning previously assigned to them.

The following examples illustrate the preparation of the azo compounds of my invention:

Example 1 and colors cellulose acetate silk and the other textile materials named herein orange.

1 gram mol of diazotized p-aminoacetophenone can be substituted for the diazoniwn compoundof the example to obtain a dye compound which similarly colors the materials above identified orange.

Example 2 1 gram mole of diazotized p-nitroaniline is coupled with 1 gram mole of m-methyl-N-phenyl- 3,5-dihydroxypiperidine. Coupling and recovery of the dye compound formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtained yields red shades.

Example 3 1 gram mole of diazotized l-amino-2-chloro-4 ultra-benzene is coupled with 1 gram mole of m-methyl-N-phenyl-3,4,5 trihydroxypiperidine. The dye compound obtained colors cellulose acetate silk rubine shades.

Example 4 1 gram mole of diazotized I-amino-Z-hydroxy- 4-nitro-benzene is added slowly to an aqueous solution of m-methoxy-N-phnyl 3,4,5 trihydroxypiperidine 'monosulfatosodium salt. Concurrently with the addition of the diazonium solution, a sodium bicarbonate solution is added at such a rate that the reaction mixture. is maintained just neutral. Upon completion of the coupling reaction which takes place, the dye compound formed is precipitated by adding sodium chloride, recovered by filtrationand dried. The

yl-3-methoxy-4,5-dihydroxy dye compound obtained colors cellulose acetate silk, wool, silk and Nylon pink shades from an aqueous solution of the dye which may contain a salt such as sodium chloride. By monosulfatosodium salt is meant that the equivalent of one hydroxyl. group is replaced by the sulfato group in its sodium salt 'form. The exact location of the monosulfato group is not known but it is probable that a partial replacement of each of the hydroxyl groupstakes place.

Ezamplc 5 lgrammoleoi OCH; H2 H1 0-0 H Z o= =0 H3 /i 0H AH: n ma on is dissolved in pyridine and treated at room temperature with 1 gram mole of The reaction which takes place is completed by warming the reaction mixture on a steam bath following which an aqueous solution of sodium bicarbonate isadded to the reaction mixture and the pyridine removed by distillation under reduced pressure. The phosphate compound formed is precipitated from the reaction mixture by the addition of sodium chloride and is recov ered by filtration.- In the reaction described the equivalent of one of the hydroxyl groups present in the 3- and'4-positions of the piperidine nucleus is converted to a group. The dye compound obtained colors the textile materials namedherein violet shades. By the use of 1 gram moleof in the above reaction in place of the reactant used the corresponding phosphite dye compound can be formed. This dye compound similarly yields violet shades.

Example 6 1 gram mole of 2,4-dinitroaniline is diazotized with nltrosyl sulfuric acid and the diazonium compound obtained is poured into water. The diazonium solution obtained is then added to a cold dilute hydrochloric acid solution containing 1 gram mole of 2-methoxy-5-acetamino-N-phenthe formula:

0 CzHs The coupling reaction which takes place is compiperidine having with 1 gram mole of pleted by adding sodium :acetate until the reaction mixture is neutral to Congo red paper. The

dye compound obtained colors cellulose acetate sill; and the other textile materials named blue.

Example 7 1 gramimoleof diazotized 1 amino-2-chloro-= 4,6-dinitrobenzene is coupled'as in Example 8 The dye compound obtained colors cellulose acetate silk blue. I

Example 8 1 gram mole of diazotized 2-amino-3,5-dinitrobenzene sulfonethylamide is coupled in an acetic acid solution with. l gram mole of The dye compound obtained colors v cellulose acetate silk reddish blue shades.

Example 9 1 gram mole of dlazotized p-nitroanillne is coupled in a hydrochloric acid solution with 1 gram mole of N-phenyl-i'iAfi-trihsrdrcxypiperidine. The dye compound obtained colors cellulose acetate silk red.

Example 10 I trihydroxypiperidine can be substituted for the coupling component of the above example, coupling being efiectedin an acetic acid solution,

- to obtain a dye'which similarly colors cellulose acetate sill: pinkish-rubine shades.

Example 11 1 gram mole of diazotised p-aminoazobensene is coupled in an acetic acid solution with 1 gram mole of N-phenyl-3,4,5-trihydroxypip ridine.

The dye compound obtainedmolors cellulose M acetate silk orange.'

It will be understood that ifdesired the paminoazobenzene can be applied to the cellulose acetate fabric, diazotized thereon and coupledwith the component just mentioned.

' Example '12 or hydrochloric acid solution with i-gram mole I V H n on c'-'ono n on.

The dye com um! obtained colors cellulose acetate silk reddish-blue. 16 Example 13 1 gram mole of dlazotized l-amino-Z-methyl- 4-nitrobenzene is'coupled in a hydrochloric aci solution with 1 gram mole of so The dye compound obtained colors. cellulose acetate silk red. 1 I

Example 14 1 gram. mole of o-methoxybenzeneazocresidine is applied to a cellulose acetate fabric (3% dyemg, for example) 'diazotized thereon and then coupled with 1 gram mole oi N-phenyl-sAfitrlhydroxyplperidine. The cellulose acetate fabric is-oolored red. 7

'1 gram mole of 4'-dimethylamino-4-aminoazobenzene can be substituted tor the o-methoxybeneazocresidine ot the example to obtain a cellulose acetate sills fabric which is colored Y 7 red.

v Example 15.

1 gram mole of is applied to the'cellulose acetate fabric (1% by weight of dye). yielding a red coloration thereon. The fabric is then washed with water following which it is treated with aqueous nitrous acid to diazotize the free amino group of the dye. Upon completion of the diazotization' reaction, the. 7 fabric is again washed and thentreated with an aqueous suspension of m-monoacetylamino-N- phenyl-4,5-dihydroxypiperidine. The cellulose acetate fabric is colored a deep Navy blue shade which can be discharged to'a pure white.

Therollowinz tabulation further illustrates the compounds .included within the scope of my in-: vention together with the colors theyproduce on cellulose acetate silk. The-compounds indicated below may be prepared by diaz'otizing the amines listed under'theheading Amine and coupling the diazonium compounds obtained with the compounds specified in the column entitled "Coupling component. The diazotization. and

TI coupling reactions may, for example, be

out following the general procedure described in Examples 1 to 15, inclusive.

N-phenyl hydromiperidine and N-naphthyl hydroxypiperidine eompoundscan be prepared 'Amine Coupling component Color Anili a l. 1 H OH Yellow.

a a a e y H A N/ \C/ c 0 on s l &\

Do 2. 0 0011. Do.

0' J; a 00m O g c on IL on Do a. n on no.

0(- g:6\ on o-f-cmcm 130-; 4. H on Do.

5' b" a n 1-1 00n J g o /0CaH| 1i o-r OCsHl g1. no.

n 011. gi c\ i 1 on OK: YNiroanfline 1 iabova Omiutorubinol-amilno-gzmdinmigo-d-(cl, Br)? I n OrannDo to blue.

my H. an l-fiinKMcetoA-nitrobifia I 0 Orange to rubine 5r1 i2o-2mminophenylmothylslfli' I: s:

It will b understood that the examples given herein .are intended to be illustrative and not limitative or my invention. Thus, any of the diazonium compounds disclosed herein can be coupled with any of the coupling components dis- .closed herein to obtain dye compounds of the invention.

Sulfonated amines which can be diazotized and the dlazonium compounds obtained coupled with any or the coupling components shown herein to obtain. dye compounds oi my inventioninclude, for example, p-sulfanilic acid, metanilic acid,'-1- amino-2-suiionic-4-nitrobenzene. disulionic benzene and 1-amino-2-chloro-4-sulionic benzene. As previously indicated, the sill ionated compounds 'are useful for the coloration of wool and silk. The compoundsprepared, for example, from diazotized p-sulifanilic acid and N-phenyl -3, 4,5-trihydrowpiperidine' yields red. shades while thatobtained from 1- amino-2-sulionic-4-nitrobenzene and m-methyl- 1-amino-2.4- ll by reacting anani1ine ,or amlno-naphthalene compound with a 1,5-dihalopentane die! or triol. Suitable aniline or aminonaphthalene compounds include those indicated by the coupling components disclosed herein. Illustrative 1,5-diha1opentane diol or. trial vcompounds include can be prepared by theaction of hypochlorous acid (HOCI) on CH:=CHCHz-CH =CH: after the direction of Chemiker Zeitung, 1914, 1 page 754. N-phenyl-3,4,5-trilnvdroxypiperidine yields rubine shad 4 fl clcmcncncncmcl in many cases stands for a member selectedfrom the group consisting of a hydroxy group, a ONH4 group, an

can be prepared by chlorinating pentane 2,3,4- triol.

It is here noted that the term Nylon refers to a linear polyamide resin which is believed to be basically described or claimed in U. S. Let ters Patent 2,071,250, issued February 16, 1937,

to Wallace H; Carothers. The term Vinyon refers to a vinyl chloride-vinyl acetate copolymer. This material is more completely identified at pages 73 and 74 of "Synthetic Organic Chemicals," th edition, published October 15, 1940, by Carbide & Carbon Chemicals Corporathe resulting paste in water.

Direct dyeing operations can, with advantage, be conducted at temperatures of about 75-85 C. but any suitable temperature may be used. Thus, the textile material to be dyed or colored is ordi- ,narily added to the dyebath at a' temperature lower than that at which the main portion of the dyeing is to be efiected, a temperature approximating Ail-55 C., for example, following which the temperature is raised to that selected for carrying out the dyemgoperation. The temperature at which the dyeing is conducted may, of course, be varied somewhat depending upon the particular material undergoing coloration. As

I is understood by those skilled in the art, the

intensity oi dyeing can be varied by varying the proportion oi dye to material undergoing coloration. Generally speaking, 1-3% by weight of dye to material is employed although any desired proportion can be used.

Suitable dispersing agents, together with the amounts that may be employed, are disclosed in McNally and Diclrey Patent No. 2,115,030, issued April 26, 1938. The process disclosed in this pat out for the dyeing of cellulose acetate silk can be used in applying the nuclear non-suiionated dyes or the present application to this material specifically as well as the other textile materials named herein. v

The nuclear sulfonated dye compounds can be applied for the dyeing of wool and 511K by-metnods known in the art for the dyeing of these materials. They can, for example, be applied directly to wool and silk by the method disclosed for the coloration of cellulose acetate $11K, except that the dye will be sumcientiy soluble as to render the use of a dispersing agent unnecessary. It is here noted that, while colors yielded by the nuclear non-sulfonated dye compounds have been given primarily with reference to cellulose acetate silk, the other materials named herein arecolored generally similar shades.

I claim:

1. The azo compounds having the formula:

the group consisting ofa benzenehucleus and an azobenzene nucleus, R1 stands for a member selected {mm the group consisting of a benzene nucleus and a naphtnaleneinucleus, X stands for a piperiaine nucleus joined through its nuclear nitrogen atom to a carbon atom of the member R1 Jvhich is in para position to the azo bond, 0Y-

alkali-forming metal, an alkoxy group, an

' O (l:Talkyl group, a sulfato group, a phosphato group and a phosphito group and n stands for a member selected from the group consisting of 2 and Band wherein no more than one of the OY groups is asulfato, a phosphato or a phosphito group.

2-. The azo compounds having the formula:

wherein R stands for a benzene nucleus, R1 stands for a member selected from the group consisting of a, benzene nucleus and a naphthalene nucleus, X stands for a piperidine nucleus joined through its nuclear nitrogen atom to a carbon atom of the member R1 which is in para position to the azo bond, OY stands for amember selected from the group consisting of a hydroxy group, an ONHA group, an 'O-alkali-forming metal, analkoxy group, an I V o-o-mkm group, a sulfate group, a phosphato group all a phosphito group and n stands for a member selected from the group consisting of 2 audit and wherein no more than one of the OY groups is an alkoxy, an

yl (I) a sulfato, a phosphato or a phosphito group.

3. The azo compounds having theformula:

wherein R stands for a benzene nucleus, R1 stands for a benzene nucleus, X stands for a piperidine nucleus joined through its nuclear nitrogen atom --f0rming metal group, an alkoxy groulban wherein R stands for a member selected from wherein no more than one of the OY groups is an alkoxy, an

a sulfate, a phosphate or a phosphito group. 4. The azo compounds having the formula: I

R -N=NR.1X--'(OH)11 wherein R stands for a member selected from thegroup consisting of a benzenenucleus and an azobenzene nucleus, R1 stands for a member selected from the group consisting of a benzene nucleus and a naphthalene nucleus, X stands for a piperidine nucleus joined through its nuclear" nitrogen atom to a. carbon atom of the member R1 which is in para position to the azo bond and it stands for a member selected from the group consistingof 2 and 3.

5. The azo compounds having the formula:

wherein R stands for a benzene nucleus, R1 stands for a member selected from the group, consisting of a benzene nucleus and a naphthalene nucleus, X stands for a piperidine nucleus joined through its nuclear nitrogen atom to a carbon atom of the member R1 which is in para position to the azo bond and n stands for a member selected from the group COIlSiStil'lg'Of 2 and 3.

6. The azo compounds having the formula:

wherein R stands for a benzene nucleus, R1 stands for a benzene nucleus, X stands for a piperidine nucleus joined through its nuclear nitrogen atom to a carbon atom of the member R1 which is in para position to the azo bond and n stands for a member selected from the group consisting of 2 and 3. r

7. The azo compounds having the formula:

wherein R stands for a member selected from the wherein Z and Z1 each stand for a member selected from the group consisting of hydrogen, a halogen atom, a nitro group, a hydroxy group,

. an alkyl group, analkoxy group, an alkylsulfone group consisting .of a benzene nucleus and an azobenzene nucleus, R1 stands for a member selected from the group consisting of a benzene nucleus and a naphthalene nucleus, X stands for wherein Z and Z1 each stand for a member selected from the group consisting of hydrogen, a halogen atom, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an alkylsulfone group, a sulfonamide-group and a carboxyl group, R1 stands for a member selected from the group consisting of a benzene nucleus and a naphthalene nucleus, X stands for a piperidine nucleus joined through its nuclear nitrogen atom to a carbon atom of the member R1 which is in para position to the azo bond, OY stands for a member selectedfrom the group consisting of a hydroxy v group, a ONH4 group, an O-alkall-forming metal group, an alkoxy group, an

o-fi-hk 0 from the group consisting of a benzene nucleus wherein no more than one orthe OY groups is a sulfato, a phosphato or aphosphito group. 9. The azo comounds having the formula:

group, a sulfonamide group and a carboxyl group, R1 stands for a benzene nucleus, X stands for a piperidine nucleus joined through its nuclear nitrogen atom to a carbon atom of the member R1 which is in para position to the azo bond, OY stands for a member selected from the group consisting of a hydroxy group, a ONH4 group, an O-alkali-forming metal group, an alkoxy group. an

group, a sulfato group, a phosphato group and a phosphito group and n stands for a member se-- lected from the group consisting of 2 and 3 wherein no more than one of the 01'' groups is an alkoxy, an 5 a sulfato, a phosphato or a phosphito group.

10. The azo compound having the formula:

12. The azo compound having the formula:

' n on it n on on 13. A cellulose acetate colored with a nuclear non-sulfonated azo dye compoundhaving the 'Iormula: 7 1 I RN=NR1X--(OY)11 wherein R stands for a member selected from the group consisting of a benzene nucleus and an azobenzene nucleus, R1 stands for a member selected and a naphthalene nucleus, X stands for a piperidine nucleus joined through its nuclear nitrogen atom to a carbon atom of themember R1 which is in para position to the azo bond, OY stands for r a member selected from the group consisting of a hydroxy group, a ONH4 group, an O-alkali-forming metal group, an alkoxy group, an

wherein no more than one of the 0? groups is an alkoxy. an

' o-c-nm a sulfato, a phosphato or a phosphito group.

14. A cellulose acetate colored with a nuclear non-suli'onated azo dye compound having the formula:

member selected from the group consisting of a hydroxy group. a ONH4 group, an O- alkali-torming metal group, an alkoxy group, an

o-o-mm group, a sulfato group, a phosphato group and a phosphito group and n stands for a member selected from the group consisting of 2 and 8 and 10 wherein no morethan one 0! the OY groups is an. alkoxy, an

O-C-alkyl 15 a suliato, a phosphate or a phosphitc group,

JOSEPH B. DIQKEY. 

